Process for polymerizing epoxides

ABSTRACT

In the polymerization of an epoxide, a high conversion of the monomer to the polymer and a high yield of solid polymer are attained by use of a new catalyst which is formed by reacting an imide with the reaction product of a hydrocarbon-aluminum compound with an ether. The amount of the catalyst required is small in comparison with the conventional processes.

United States Patent Hani et al.

[54] PROCESS FOR POLYMERIZING EPOXIDES [72] Inventors: lllroshl Hull; Yasushl Muuda, both of Kanagawa-ken, Japan [73] Assignee: Asahi Glass Co., Ltd., Tokyo, Japan [22] Filed: Sept. 25, 1969 [21] Appl. No.: 862,162

[30] Foreign Application Priority Data Oct. 4, 1968 Japan ..43/7l840 [52] US. Cl. ..260/2 A, 252/431, 260/615 B 511 lnLCl. ..C08g23/06,C08g23/l4 [581FieldoiSearch ..260/2,615B

[ 1 Feb. 22, 1972 References Cited UNITED STATES PATENTS 3 .05 8,922 10/ l 962 Vandenberg ..26()/2 3 .05 8,923 lO/ 1 962 Kutner ..260/2 3,186,958 6/1965 Kutner et al ..260/2 Prir nary Examiner-William M. Short Assistant Examiner-E. Nielsen Attorney-Kurt Kelman [57] ABSTRACT 12 Claims, No Drawings PROCESS FOR POLYMERIZING EPOXIDES BACKGROUND OF THE INVENTION This invention relates to a new process for polymerizing epoxides and, more particularly, to a new process for homopolymerizing or copolymerizing at least one kind of epoxide in the presence of a new catalyst.

In recent years the homopolymers and copolymers of various epoxides such as ethylene oxide, propylene oxide and epichlorohydrin have been used in such applications as rubber articles. For example, they have excellent in weather resistance, oil and solvent resistance, impermeability to gases and ozone resistance. For producing such epoxide polymers, there are several known processes wherein one or more epoxide monomers are polymerized in the presence of a catalyst which is obtainable by reacting an organoaluminum compound with water or a chelating agent (U.S. Pat. Nos. 3,135,705 and 3,135,706) or a catalyst obtainable by reacting a hydrocarbon aluminum compound with a basic nitrogencontaining compound (U.S. Pat. No. 3,186,958). However, in those polymerization processes, neither the conversion of epoxide monomers to polymers nor the yieldof solid high polymers is always as high as might be desired. Furthermore, in the conventional polymerization processes, the amount of the organoaluminum catalyst required actually amounts to several molar percent or more based on the epoxide monomer. The outcome is that the method involves the use of large amounts of the organoaluminum compound which is expensive, and this results in a considerable increase in the cost of commercial production of epoxide polymers.

SUMMARY OF THE INVENTION It is an object of the invention to provide a novel process for polymerizing epoxides in the presence of a new catalyst which is not known to the prior art.

Another object is to provide a new process for polymerizing epoxides, wherein the amount of the catalyst required is relatively small as compared with the conventional art.

Still another object is to provide a new process for polymerizing epoxide which yields epoxides polymers-having satisfactory rubberlike elasticity.

Other objects of the invention will be apparent from the detailed description of the invention that follows.

DETAILED DESCRIPTION OF THE INVENTION After extensive work on the polymerization of epoxides with a view of improving the conventional processes, we have discovered a process for polymerizing epoxides advantageously on a commercial scale by the use of a new catalyst which differs from the conventional organoaluminum catalysts.

Thus, we found that the catalyst obtainable by reacting a hydrocarbon aluminum compound with an ether andreacting the resulting reaction product with an imide shows an extremely high activity for the polymerization of epoxides.

It was also found that when epoxides are polymerized in the presence of such a catalyst, a high conversion rate is attained and that this high conversion of the monomer to the polymer is accomplished using a relatively small amount of the catalyst as compared with the conventional processes. In addition, it was further discovered that by varying the types of ether used in the preparation of the catalyst, it is possible to produce polymers having varied properties from amorphous rubberlike polymers to crystalline polymers. This invention is the culmination of the foregoing discoveries.

Thus, the present invention relates to a process for homopolymerizing or copolymerizing one or more different epoxides in the presence of a catalyst obtainable by the reaction of an imide with the reaction product of hydrocarbon aluminum compound and an ether.

The new catalyst to be employed in the polymerization process according to this invention is prepared in the following manner. In the first place, any hydrocarbon aluminum compound having the formula AiR where at least one R is a hydrocarbon radical and remaining Rs are hydrogen or hydrocarbon radical may be used in this invention. Exemplary of these hydrocarbon aluminum compounds are trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridodecylaluminum, etc., alkylaluminum hydrides such as diethylaluminum hydride, dimethylaluminun hydride, diisobutylaluminum hydride, etc., the corresponding alkenyl, cycloalkyl, cycloalkenyl, aryl and aralkyl aluminum compounds as, for example, triisopropenylaluminum, tricyclohexylaluminum, tricyclohexenylaluminum, triphenylaluminum, tribenzylaluminum, etc., or a mixture of these aluminum compounds.

The ether mentioned above may be a cyclic ether having a four-tosix membered ring such as cyclooxabutane, tetrahydrofuran, tetrahydropyran, dioxane or dioxolan, a linear ether such as diethylether, diisopropylether, anisole, phenetol, diphenylether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or triethylene glycol dimethyl ether, a substitution product of any of such cyclic and linear ethers, or a mixture of the aforesaid ethers.

The aforesaid reaction product of a hydrocarbon aluminum compound with an ether is obtained by reacting a hydrocarbon aluminum compound with one of the ethers given above. The structure of this reaction product remains yet to be thoroughly elucidated, but it is reasonable to assume from the information provided in J. Am Chem. Soc, 64, 316 (1942) that it is the addition product of the hydrocarbon aluminum compoundand the ether used. In any event, the aforesaid reaction product is obtained when said hydrocarbon aluminum compound is mixed with said ether. Those reactants may be reacted on an equimolar basis, or either of them may be used in excess. However, the preferred molar ratio of the ether to the hydrocarbon aluminum compound ranges from about 0.3 to 20 and, for better results, from about 1 to 7.

When the'above reaction is effected-outside of the first mentioned range, the activity of the catalyst attainable according to this invention is greatly reduced, if not completely erased. It has also been found that the final catalyst has a higher activity when the ether to be reacted with the hydrocarbon aluminum compound is a cyclic rather than a linear ether.

The resulting reaction product of hydrocarbon aluminum compound and ether is then reacted with an imide either directly or after the unreacted materials are removed from the reaction mixture. As the aforesaid imide, any cyclic imide or its derivatives which are derived from dibasic carboxylic acid may be used. Exemplary of these imides 'or their derivatives are succinimide, glutarimide, adipimide, maleinimide, malonimide and phthalimide or their hydrocarbon substitution products or N-halogen-substitution products. These imides are employed either singly or in combination. The amount of the imide to be reacted with the aforesaid reaction product of a hydrocarbon aluminum compound and an ether is critical and must be within a range from 0.01 to 2 moles per mole of the hydrocarbon aluminum compound and, preferably, 0.1 to 1 mole on the same basis. And the reaction of an imide with the reaction product of an hydrocarbon aluminum compound and an ether is usually carried out within the temperature range of 0 to 200 C. and, preferably, from room temperature to C., either in the absence of a'solvent or in a solvent inert to the reaction, for example suitable hydrocarbons such as benzene, toluene, n-heptane, cyclohexane etc., or a halogenated hydrocarbon such as chlorobenzene, carbon tetrachloride etc. A feature of the reaction of the reaction product of said hydrocarbon aluminum compound and ether with said imide is that the color of the reaction mixture changes with the progress of the reaction. In contrast, when the same hydrocarbon aluminum compound is directly reacted with the same imide as above, the color assumed by the reaction mixture immediately upon the admixing .of the reactants remains unchanged throughout the reaction.

The change in color of the reaction mixture is rather pronounced, and it has been found that, if the reaction mixture before it undergoes such a color change is used as the catalyst, its activity is extremely low. On the other hand, the

bulk polymerization, for the purpose of controlling the temperature, it is permissible to conduct the reaction under reflux at the boiling point of the epoxide monomer.

The polymerization temperature ranges from l to same reaction mixture gives a high catalytic activity if it is 5 +200 C. and,preferably 0 to 100 C. used after a sufficient degree of color change has taken place. While the reaction is usually carried out under autogenous Therefore, this color change can be made use of not only as a pressure. it may be conducted at pressures up to about 200 atmeasure with which the endpoint of the r a tion f th reac. mospheres, if required. it is also possible to carry out the reaction product of a hydrocarbon aluminum compound an an tion under reduced Pressureether with the imide can be ascertained but also as a yardstick The Process of the invention is characterized the with which the activity of the resulting catalyst can be deteramount of Catalyst required is much lower than required mined. While the time required for the color change of the in the cohvemioha] processes- Thus it has been Confirmed reaction system to t k place d d upon h types f that the amount of the catalyst required in this invention is sufcatalyst components and the reaction temperature, it usually ficiem in the range from -9 to 05 P base? on takes from a few mi t to a f hours epoxy monomer used. This range represents a considerable In the preparation of the catalyst according to this i reduction from the effective amount of the conventional ortion, it has been found that the reaction between a hydrocargahoalumihum compound catalysl- Howeverr catalyst bon aluminum compound and an ether is considerably more cording to the invention y he used in larger amounts, P to rapid than the reaction between the same hydrocarbon aluabout 10 Percent based on the epoxy mohomel" The minum compound with an i id Th f h amount of the catalyst required depends upon the type and aforedescribed procedure of mixing the hydrocarbon alupurity of the epoxide, the purity of the inert diluent being used minum compound with the ether and, then, reacting the imide and other faCtOfS- For ample, the epoxides of low purity with the mixture is not al mandatory F instance, h I require a larger amount of the catalyst. In this connection, in catalyst according to this invention may be prepared b dorder that as small an amount of the catalyst as possible will ding the ether and imide simultaneously to the hydrocarbon suffice, the starting material is preferably as pure as possible. aluminum com ound, Howev if th th i dd d l of ll However, in accordance with the invention, since the activity the three components, e.g., if the ether i dd d to th reacof the catalyst is considerably higher than the conventional tion mixture of said hydrocarbon l i compound d catalysts, even a starting material containing somewhat larger imide, the aforementioned reaction product of hydrocarbon amounts f impurities may be employed satisfactorily without aluminum compound and ether is not formed and, ac- Preliminary Purificationcordingly, the resulting catalyst has only a quite inadequate The homopolymer or p y of one or epoxides activity. which are thus obtainable according to this invention has vary- Furthermore, the catalyst according to this invention should ing pr p rtie r nging fr m one which i r erlike to a be contacted with the epoxide monomer only after it has been crysta i e P p ng p the yp of elher Used in prepared. This is due to the fact that the reaction of the reaccatalyst The form" yp of Product has an extensive tion product of a hydrocarbon l i compound d an range of applications, such as lube oil additives, wax additives, ether with an imide is relatively slow as previously mentioned. adhesive mp n after g, in g hoses Any epoxides may be homopolymerized or copolymerized and other formed articles. On the other hand, the latter with a second epoxide by the process of this invention. Out- 40 crystalline product is useful as a material in the manufacture standing results are obtained with epoxides wherein the epoxy of Plastics, film formers and fibersgroup is an oxirane ring such as ethylene oxide, propylene ox- The following examples are further illustrative of the invenide, butylene oxide, epichlorohydrin, epibromohydrin, tion. it should be understood that the invention should by no epifluorohydrin, n-butene oxide, styrene oxide, allylglycidyl means be construed as being limited y those examples, but ether. phenylglycidyl ether, cyclohexeneoxide, ermany changes and modifications may be made without departfluoroethylene oxide, perfluoropropylene oxide, et ing from the scope and spirit of the invention described in the The polymerization reaction may be conducted either pp Claimsbatchwise or continuously, and any'suitable reaction vessel can be utilized for the purpose. The epoxide monomer and the EXAMPLES l-3 TABLE 1 Conversion of Characteristics epichloroof epichloro- Example Color of hydrin hydrin number Type of imide liquid catalyst (percent) polymer 1 Succinimide Yel1owlshorange. 100 Rubbery. Control. 12 Non elastic. 2 97 Rubbery. Control. .-do Yellowish orange.- Non elastic.

N-ehlorosuccinlmide. Blue black 82 Rubbery. Control do Pale yellow 9 Non elastic.

catalyst may be introduced simultaneously into the reactor, or one after the other. it is permissible to add either of them in a single batch, continuously over the polymerization period or in several installments. The polymerization reaction according to this invention may be conducted in the presence of an inert diluent or in the manner of bulk polymerization. The inert diluent mentioned just above may be any diluent that will remain inert under the polymerization conditions. For example, hydrocarbons such as benzene, toluene, n-heptane, cyclohexane etc., halogenated hydrocarbons such as carbon tetrachloride, chlorobenzene etc., ethers such as diethylether, dipropylether, dioxane, etc., may be mentioned. 1n the case of In these examples, as well as in the examples that follow, all the reactions were carried out in nitrogen gas streams. l mole/l of a solution of triisobutylaluminum in toluene was mixed with a molecular equivalent of dioxane at room temperature whereupon a reaction mixture containing the reaction product of the triisobutylaluminum and dioxane was obtained. This reaction mixture was mixed with 0.25 molar equivalent of one of the imides shown in Table l at 40 C. for 1 hour, whereupon a liquid catalyst was obtained. On the other hand, -a reactor was charged with l2.9 g. epichlorohydrin and 65 g. chlorobenzene, followed by the addition of 28 millimole, relative to the aluminum, of the aforesaid liquid catalyst. With the reactor being maintained at a temperature of 30 C., the reaction was allowed to continue for about 24 hours. The contents were withdrawn and stirred .with ethanol, whereupon a solid polymer was obtained. This solid polymer was immersed in ethanol containing 0.5 percent of 4,4-thio-biso-t-butyl-m-cresol, and, dried under reduced pressure. Table l shows the types of imide used, the color of the liquid catalysts obtained, the conversion of epichlorohydrin and the characteristics of the resulting epichlorohydrin polymers in those examples. As controls, the reaction mixtures prepared by reacting triisobutylaluminum with the various imides without use of dioxane, were used as catalysts and the reactions were conducted under the same conditions as above. The results are also shown in Table 1.

It will be apparent from Table 1 that compared with the controls, those examples of the invention give much higher conversions of epichlorohydrin monomer to epichlorohydrin polymer, that the resulting epoxide polymers are amorphous and that the colors of the liquid catalysts differ considerably from those of the control catalysts.

EXAMPLES (controls) 4-7 Epichlorohydrin was polymerized under the same conditions as in Example 1, except that the various nitrogen-containing compounds (N compd.) given in Table 2 were used in place of an imide. The results are set forth in Table 2. 1n the controls of Table 2, no dioxane was used, as in the controls of Table 1.

The color of the reaction mixture of the example and its corresponding control was almost same.

It will be apparent from Table 2 that without the use of dioxane in the catalyst no high molecular weight polymer is obtained in high yield.

- EXAMPLES 11-12 Triisobutylaluminum, dioxane and succinimide were mixed together in the same molar ratios, for the same reaction times and in the same sequences as Examples 1 and 2, at the temperatures shown in Table 4.

Using the resulting liquid catalysts, the polymerization reactions were respectively carried out under otherwise the same conditions as Example 1. Table 4 shows the temperatures at which the catalysts were prepared, the colors of the resulting liquid catalysts, conversion of epichlorohydrin and the characteristics of the resulting epichlorohydrin polymers. The control catalyst was prepared without use of dioxane. Thus, the reaction mixture of triisobutylaluminum and succinimide was directly employed and the polymerization reaction was conducted under otherwise the same conditions as the above examples of this invention.

1 At which catalyst was prepared.

As to the control, there is observed no variation in result 7 due to changes in the temperature at which the catalysts were prepared. In contrast, it will be seen that in the case of the catalysts according to the invention, both the activity of the EXAMPLES 810 Triisobutyl aluminum, dioxane and succinimide were reacted at C. in the molar ratios and sequences set forth in Table 3. In each example, using 0.5 mole percent, based on the triisobutylaluminum, of the resulting liquid catalyst and, as a diluent, chlorobenzene, the polymerization was conducted at 30 C. The initial concentration of epichlorohydrin was 2 mole/I. The reaction rates of epichlorohydrin in these examples are shown in Table 3. Incidentally, the reaction sequences of catalyst components in Table 3 were such that, taking Example 8 as an example, succinimide and dioxane, which are bracketed, were previously mixed together in the molar ratio of 0.25 to 3.0 and the resulting solution was further mixed with 1.0 mole and triisobutylaluminum based on 0.25 mole of succimide contained in said solution. The same applies to the control.

catalysts and the crystallinity of the epichlorohydrin polymers are markedly changed by the temperature at which the catalysts are prepared.

EXAMPLES 13-14 Except that the catalyst preparation temperature was held at 40 C. and the time of the reaction (catalyst preparation time) of the reaction product of triisobutylaluminum and dioxane with succinimide was varied, epichlorohydrin was Color of liquid catalyst Conversion epichlorohydrin (-1) Catalyst preparation time (min.

Example 12 Pale 12 yellow Pale yellow Reddish orange Pale yellow Regarding the controls, substantially no change was observed due to the change in catalyst preparation time. In contrast, the case of the catalyst according to the invention, the catalyst activity was markedly enhanced with the increase in catalyst preparation time.

EXAMPLES (controls) ll8 0.7 millimole triisobutylaluminum, 0.018 g. succinimide and 12.9 g. epichlorohydrin were reacted together with various propositions of chlorobenzene and dioxane as set forth in Table 6 in a varying sequence also shown in the same table. The reaction was conducted at the temperature of 30 C. for 24 hours. The sequences of mixing the aforesaid components, the amounts of chlorobenzene and dioxane added and the conversion ofepichlorohydrin are set forth in Table 6.

to a mixture ofCB, DOX, ECH and AI In Table 6, CB denotes chlorobenzene, DOX dioxane, Sl succinimide, ECH epichlorohydrin and AI triisobutylaluminum.

It will be seen from Table 6 that if any one of the catalyst components is added after the addition of epoxide monomer, the catalyst activity invariably is considerably low.

EXAMPLE 19 The reaction product of triisobutylaluminum with 3 molar equivalents of dioxane was mixed with 0.25 molar equivalent of succinimide and the mixture was allowed to react at 70 C. for 1 hour. A reactor was supplied with 46.3 g. epichlorohydrin, followed by the addition of 25 millimole based on the aluminum, of the liquid catalyst prepared above. The polymerization was started with a vigorous evolution of heat at the moment of the mixing. Then, the reaction was continued at the temperature of 30 C. for about 24 hours. The resulting reaction mixture containing an epichlorohydrin polymer was treated in the same manner as in Example I, whereupon l4.l g. of solid polyepichlorohydrin was obtained.

EXAMPLE 20 The preparation was conducted in the same manner as in Example 15, except that diisobutylaluminum hydride was used in place of triisobutylaluminum. A reactor were supplied with 12.9 g. epichlorohydrin and 65 g. chlorobenzene, followed by the addition of 2.8 millimole, based on the aluminum, of the liquid catalyst prepared above. The polymerization was started with a vigorous evolution of heat at the moment of the mixing. Then, the reaction was continued at the temperature of 30 C. for about 24 hours. The resulting reaction mixture containing an epichlorohydrin polymer was treated in the same manner as in Example 1, whereupon 7.3 g. of solid polyepichlorohydrin was obtained.

EXAMPLES 2l-30 Epichlorohydrin was polymerized under the same conditions as in Example 1, except that the various ethers given in Table 7 were used in place of dioxane. The results are set forth in Table 7. It will be apparent from Table 7 that in the process of the invention. the characteristics of the epichlorohydrin polymer can be modified as desired by using different types of ether.

TABLE 7 Conversion cpichloro- Characteristics Example Types of hydrin ofepichloro- No. ether '1' hydrin polymer 2l Tetrahydrofuran Crystalline 22 Tetrahydrofuran 37 Amorphous 23 2-Methyltetra l6 Amorphous hydrofuran 24 m-Dioxane l5 Amorphous 25 Ethyl ether l2 Crystalline 26 Ethylene glycol 52 Amorphous dimethyl ether 27 Diethylene glycol 13 Amorphous dimethyl ether 28 Triethylene glycol 12 Amorphous dimethyl ether EXAMPLE 29 A reactor was supplied with 5.3 g. ethylene oxide and 59.3 g. chlorobenzene, followed by the addition of 0.7 millimole, relative to the aluminum, of the catalyst prepared in the same manner as Example 1. The reaction was continued at the temperature of 30 C. for about 24 hours. At the end of the reaction time the contents of the reactor were stirred with a large excess of petroleum ether. The above procedure yielded a solid polyethylene oxide. The yield of the polyethylene oxide was 69 percent on a dry-weight basis.

EXAMPLE 30 A l mole/l solution of triisobutylaluminum in toluene was mixed with a molar equivalent of tetrahydrofuran at room temperature, followed by the addition of 0.25 molar equivalent of succinimide. The reaction was conducted at 40 C. for 1 hour to prepare a liquid catalyst. A reactor was supplied with 81 g. propylene oxide and 66 g. chlorobenzene, followed by the addition of 0.7 millimole, relative to the aluminum, of the above liquid catalyst. The reaction was allowed to continue at 30 C. for about 24 hours. At the end of the reaction time steam was introduced into the contents of the reactor to purge the chlorobenzene and unreacted propylene oxide. The residue was dried at 60 C. and under reduced pressure. The yield of the product polypropylene oxide was 2.3 g.

EXAMPLE 3] A 1 mole/[ solution of triisobutylaluminum in toluene was mixed with 3 molar equivalents of dioxane at room temperature, followed by the addition of 0.25 molar equivalent of succinimide. The reaction was allowed to continue at 60 C. for 1 hour to obtain a liquid catalyst.

A reactor was supplied with 6.5 g. epichlorohydrin, 4.l g. propylene oxide and 65 g. chlorobenzene, further followed by the addition of 0.7 millimole, relative to the aluminum, of the above liquid catalyst. The mixture was reacted at the temperature of 30 C. for about 24 hours. At the end of the reaction time steam was forced into the contents of the reactor to purge the unreacted monomers and chlorobenzene, whereupon a solid polymer was obtained. This product was dried at 60 C. under reduced pressure to obtain 0.8 g. of an epichlorohydrin-propylene oxide copolymer.

EXAMPLE 32 The reaction mixture of triisobutyl aluminum with 3 molar equivalents of dioxane was further mixed with 0.25 molar equivalent of succinimide, and the mixture was reacted at 40 C. for 1 hour. A reactor of 3 1. capacity was charged with 2,300 g. chlorobenzene and 462 g. epichlorohydrin, followed by the addition of 25 millimole, relative to the aluminum, of the above catalyst.

The reaction was conducted at the temperature of 30 C. for 22 hours, and the resulting reaction mixture containing an epichlorohydrin polymer was treated in the same manner as in Example 1. The conversion of the monomer to the epichlorohydrin polymer was 87 percent. The reduced specific viscosity (R.S.V.) of the epichlorohydrin polymer as measured in nitrobenzene at 30 C. was 10.7 d"/g.

The epichlorohydrin polymer obtained above was compounded with the agents shown in Table 8 using an open roll. The resulting compound was press-vulcanized at 155 C. for 45 minutes. The physical properties of the cured product are set forth in Table 8. It will be seen that the product has excellent properties.

TABLE 8 l. Formulation Polyepichlorohydrin 100 parts Fast extruding furnace black 50 parts Nickel dibutyl-dithio-carbamate 1 parts Red lead parts Z-Mercaptimiclazoline 1.5 parts ll. Physical Properties Tensile strength 188 kg-ICm. Elongation at break 220% Modulus at 100% 74 kgJem. Permanent set (100% elongation) 1% or less Aged at 150 C. for 72 hrs.

Tensile strength 205 kg./cm" Elongation at break 160% Weight change in water 0.7% in ASTM No. 3 oil +20.47r

What is claimed is:

l. A process for polymerizing monoepoxides, wherein the epoxy group is an oxirane ring comprising the step of homopolymerizing or copolymerizing one or more of said monoepoxides, in the presence of a catalyst formed by reacting a cyclic imide selected from the group consisting of succinimide, glutarimide, adipimide, maleinimide, malonimide phthalimide, and N-halogen substitution products thereof with the reaction product of a hydrocarbon aluminum compound selected from the group consisting of trialkyl aluminums and dialkylalurninums with an ether selected from the group consisting of cyclooxabutane, tetrahydrofuran, tetrahydropyran, dioxane, dioxolan, diethylether, diisopropylether, anisole, phenetol, diphenylether, ethylene, glycol dimethylether, diethylene glycol dimethylether, and triethylene glycol dimethylether.

2. A process as claimed in claim 1, wherein said reaction product is prepared by reacting said hydrocarbon aluminum compound with said ether in the molar ratio of 120.3 to 20 on the basis of hydrocarbonaluminum compound.

3. A process as claimed in claim 1, wherein the molar ratio of said reaction product of hydrocarbon aluminum compound and ether to said imide ranges from 0.01 to 2 based on the hydrocarbon aluminum compound contained in said reaction product.

4. A process as claimed in claim 1, wherein the reaction between said hydrocarbon aluminum compound and ether and the reaction between the resulting reaction product and imide are carried out in the presence of an inert diluent selected from the group consisting of hydrocarbons and halogenated hydrocarbons.

5. A process as claimed in claim 1, wherein said hydrocarbon aluminum compound is a member selected from the group consisting of triisobutyl aluminum and diisobutylaluminum hydride.

6. A process as claimed in claim 1, wherein said ether is a member selected from the group consisting of dioxane and tetrahydrofuran.

7. A process as claimed in claim I, wherein the reaction mixture of said imide with said reaction product of a hydrocarbon aluminum compound and an ether is used as the catalyst only after it has undergone a change'in color.

8. A process as claimed in claim 1, wherein the catalyst is used in an amount ranging from 0.05 to about 10 molar percent on the basis of the hydrocarbon aluminum compound used relative to the epoxide monomer.

9. A process as claimed in claim 1, wherein the polymerization reaction is conducted at a temperature of from l00 to +200 C. and under the pressure of from 0.01 to 200 atmospheres.

10. A process as claimed in claim 1, wherein a member selected from the group consisting of ether, hydrocarbons and halogenated hydrocarbons is used as an inert diluent for the polymerization reaction.

11. A process as claimed in claim 1, wherein the epoxide is selected from the group consisting of epichlorohydrin, ethylene oxide and propylene oxide.

12. A process which comprises polymerizing epichlorohydrin in the 3presence of, relative to the epichlorohydrin monomer, to 7 percentby mole of a catalyst obtained by the reaction of the reaction product of triisobutylaluminum and dioxane with succinimide in the molar ratio of 1:01 to l on the basis of the triisobutylaluminum.

t a 4K UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent: o- 3 644 224 I Dated February 22', 1972 Inventor(s) Hiroshi Hani et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 3, cancel line 2; line 3, change fend ether to" to -ofand after "imide" insert -to said reaction product of hydrocarbon aluminum compound and ether- Signed and sealed this 25th day of July 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents FORM po'wso (10-69) uscoMM-Dc 60376-P69 U.S. GOVERNMENT PRINTING OFFICE I969 0-366-334 

2. A process as claimed in claim 1, wherein said reaction product is prepared by reacting said hydrocarbon aluminum compound with said ether in the molar ratio of 1:0.3 to 20 on the basis of hydrocarbonaluminum compound.
 3. A process as claimed in claim 1, wherein the molar ratio of said reaction product of hydrocarbon aluminum compound and ether to said imide ranges from 0.01 to 2 based on the hydrocarbon aluminum compound contained in said reaction product.
 4. A process as claimed in claim 1, wherein the reaction between said hydrocarbon aluminum compound and ether and the reaction between the resulting reaction product and imide are carried out in the presence of an inert diluent selected from the group consisting of hydrocarbons and halogenated hydrocarbons.
 5. A process as claimed in claim 1, wherein said hydrocarbon aluminum compound is a member selected from the group consisting of triisobutyl aluminum and diisobutylaluminum hydride.
 6. A process as claimed in claim 1, wherein said ether is a member selected from the group consisting of dioxane and tetrahydrofuran.
 7. A process as claimed in claim 1, wherein the reaction mixture of said imide with said reaction product of a hydrocarbon aluminum compound and an ether is used as the catalyst only after it has undergone a change in color.
 8. A process as claimed in claim 1, wherein the catalyst is used in an amount ranging from 0.05 to about 10 molar percent on the basis of the hydrocarbon aluminum compound used relative to the epoxide monomer.
 9. A process as claimed in claim 1, wherein the polymerization reaction is conducted at a temperature of from -100* to +200* C. and under the pressure of from 0.01 to 200 atmospheres.
 10. A process as claimed in claim 1, wherein a member selected from the group consisting of ether, hydrocarbons and halogenated hydrocarbons is used as an inert diluent for the polymerization reaction.
 11. A process as claimed in claim 1, wherein the epoxide is selected from the group consisting of epichlorohydrin, ethylene oxide and propylene oxide.
 12. A process which comprises polymerizing epichlorohydrin in the presence of, relative to the epichlorohydrin monomer, 3 to 7 percent by mole of a catalyst obtained by the reaction of the reaction product of triisobutylaluminum and dioxane with succinimide in the molar ratio of 1:0.1 to 1 on the basis of the triisobutylaluminum. 